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- W4322010426 abstract "N2O isotopic composition, i.e., δ15N-N2O, δ18O-N2O and especially site preference (SP; difference of substitution frequencies at terminal or central position in N-N-O molecule) has been shown to provide information on N2O source processes, and allows for source partitioning of N2O emissions to nitrification and denitrification. The advent of laser spectrometers more than a decade ago has spawned first datasets of N2O isotopic composition in daily resolution, but they have remained scarce. This is because until recently, the precision of commercially available spectrometers did not allow direct determination of N2O isotopic composition without technically challenging liquid nitrogen free cryogenic preconcentration of N2O. The specifications of the latest commercially available spectrometers promised preconcentration free in-situ determination of N2O isotopic composition, but a recent instrument intercomparison showed that for most of the analyzers, specific correction functions are still necessary. While some available instruments were thoroughly characterized with regard to short term precision, repeatability, drift, amount effects, matrix effects and spectral interferences, instrument performance during field deployment and on the time scale of long measurement campaigns has not been analysed so far.Here we present a setup and results of an automated chamber system in conjunction with a laser spectrometer that was installed in the field and in use for a period of approx. two years. Initially, amount dependence was in the range of 4 to 2 ‰ ppm N2O-1 for the various isotopic species, but instrument optimizations reduced this dependence to less than 1 ‰ ppm N2O-1. CH4 dependence was constant through the whole period and in the range of 1 to 2 ‰ ppm CH4-1, with affecting only δ15Nα and δ18O. In contrast, CO2 dependence was variable and in the same range as N2O amount dependence. The uncertainty budget was dominated by instrument noise, calibration and N2O amount dependence, indicating that improvements of instrument precision and availability of more suitable reference materials have a high potential to further decrease uncertainty of measurements. Analysis of the effect of uncertainty on the error of determined soil air N2O isotopic composition based on Keeling plots resulted in an error of 2 ‰ and 1 ‰ at N2O concentration increases of 70 and 140 ppb, respectively. Consequently, source partitioning based on SP will be associated with an error of 17 and less than 12% at the moment. Compared to growing-season emissions, SP and δ18O-N2O during freeze-thaw cycles were distinctly different. SP was ~0, indicating that N2O reduction to N2 was negligible during freeze-thaw events." @default.
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- W4322010426 date "2023-05-15" @default.
- W4322010426 modified "2023-09-29" @default.
- W4322010426 title "Intramolecular N2O isotopic composition using laser spectrometers: Correction functions, uncertainty budget, freeze-thaw events and source process identification" @default.
- W4322010426 doi "https://doi.org/10.5194/egusphere-egu23-12962" @default.
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